Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
  • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
  • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
  • C09K11/7715—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals containing cerium
  • C09K11/7716—Chalcogenides
  • C09K11/7718—Chalcogenides with alkaline earth metals
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
  • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
  • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
  • C09K11/7728—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals containing europium
  • C09K11/7729—Chalcogenides
  • C09K11/7731—Chalcogenides with alkaline earth metals
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/12—Light sources with substantially two-dimensional [2D] radiating surfaces
  • H05B33/14—Light sources with substantially two-dimensional [2D] radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
  • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
  • H10H20/80—Constructional details
  • H10H20/85—Packages
  • H10H20/851—Wavelength conversion means
  • H10H20/8511—Wavelength conversion means characterised by their material, e.g. binder
  • H10H20/8512—Wavelength conversion materials
  • H10H20/8513—Wavelength conversion materials having two or more wavelength conversion materials
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
  • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
  • H10H20/80—Constructional details
  • H10H20/85—Packages
  • H10H20/851—Wavelength conversion means
  • H10H20/8511—Wavelength conversion means characterised by their material, e.g. binder
  • H10H20/8512—Wavelength conversion materials
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
  • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Definitions

• the present invention relates to a tri-color lamp.
• the lamp comprises a mixture of two phosphors and a light emitting diode for an excitation energy source.
• the lamp employs a blue LED and a mixture of red and green phosphors for the production of white light.
• Phosphors are luminescent materials that can absorb an excitation energy (usually radiation energy) and store this energy for a period of time. The stored energy is then emitted as radiation of a different energy than the initial excitation energy.
• excitation energy usually radiation energy
• down-conversion refers to a situation where the emitted radiation has less quantum energy than the initial excitation radiation.
• Stokes shift the energy wavelength effectively increases, and this increase is termed a "Stokes shift.”
• Up-conversion refers to a situation where the emitted radiation has greater quantum energy than the excitation radiation (“Anti-Stokes shift").
• Improvements in efficiency and color quality in phosphor-based devices are constantly being developed.
• Efficiency relates to a fraction of photons emitted with respect to a number of photons initially provided as excitation energy. Inefficient conversion results when at least a portion of the energy is consumed by non-radiative processes.
• Color "quality” can be measured by a number of different rating systems.
• Chromaticity defines color by hue and saturation.
• CIE is a chromaticity coordinate system developed by Commission Internationale de l'Eclairage (international commission on illumination). The CIE Chromaticity Coordinates are coordinates that define a color in "1931 CIE" color space.
• These coordinates are defined as x, y, z and are ratios of the three standard primary colors, X, Y, Z (tristimulus values), in relation to the sum of the three tristimulus values.
• a CIE chart contains a plot of the x, y and z ratios of the tristimulus values versus their sum.
• a two-dimensional CIE (x, y) plot is used.
• White-like colors can be described by a "correlated color temperature" (CCT). For example, when a metal is heated, a resulting light is emitted which initially glows as a red color.
• CCT correlated color temperature
• the emitted light shifts to higher quantum energies, beginning with reddish light and shifting to white light and ultimately to a bluish-white light.
• a system was developed to determine these color changes on a standard object known as a blackbody radiator. Depending on the temperature, the blackbody radiator will emit white-like radiation. The color of this white-like radiation can then be described in the CIE chromaticity chart.
• the correlated color temperature of a light source to be evaluated is the temperature at which the blackbody radiator produces the chromaticity most similar to that of the light source. Color temperature and CCT are expressed in degrees Kelvin.
• a "color rendering index” (CRI) is established by a visual experiment. The correlated color temperature of a light source to be evaluated is determined. Then eight standard color samples are illuminated first by the light source and then by a light from a blackbody having the same color temperature. If a standard color sample does not change color, then the light source has a theoretically perfect special CRI value of 100.
• a general color rendering index is termed "Ra”, which is an average of the CRIs of all eight standard color samples.
• Older white lamps involved emission of light over a broad wavelength range. It was then discovered that a white-like color can be simulated by a mixture of two or three different light colors, where each emission comprised a relatively narrow wavelength range. These lamps afforded more control to manipulate the white color because emissive properties (emission energy and intensity) of the individual red, green and blue light sources can be individually tailored. This method thus provided the possibility of achieving improved color rendering properties.
• An example of a two-color lamp comprises one phosphor and an excitation energy source. Light emitted by the phosphor combines with unabsorbed light from the excitation source to produce a white-like color. Further improvements in fluorescent lamps involved three different light colors (i.e. a tri-color lamp) resulting in white light at higher efficiencies.
• a tri-color lamp involved blue, red and green light- emitting phosphors.
• Other previous tri-color lamps comprised a combination of light from two phosphors (a green and red phosphor) and unabsorbed light from a mercury plasma excitation source.
• the device further comprises a composition comprising a mixture of a first phosphor and a second phosphor.
• Each phosphor comprises a host sulfide material and a rare earth dopant and the composition is positioned in the light pattern.
• Another aspect of the present invention provides a device comprising a green phosphor and a blue light emitting diode, for providing an excitation radiation to the phosphor.
• FIG. 1 shows an overlay of normalized spectra of SrGa 2 S :Eu and SrS:Eu upon excitation by a blue LED at 460 nm;
• FIG. 2 shows a simulation of spectra of a mixture of SrGa 2 S 4 :Eu and SrS:Eu upon excitation by a blue LED at 460 nm at different color temperatures;
• FIG. 3 shows a schematic of a tri-color lamp comprising a two-phosphor mixture positioned in a pathway of light emitted by an LED.
• the invention relates, in part, to the discovery that a tri-color lamp employing specific red and green phosphors excitable by a common light emitting diode (LED) can achieve white light at higher efficiencies with superior color rendering over previous fluorescent lamps.
• One aspect of the present invention provides a composition comprising a mixture of a first phosphor and a second phosphor, each phosphor capable of being excited by a common light emitting diode, i.e. only one light emitting diode is used to excite both phosphors, as opposed to each phosphor requiring a separate energy source.
• An advantageous feature of the present invention involves the use of an LED as an excitation source.
• An LED has a p-n junction between doped semiconductor regions. Upon application of a current, there can exist sufficient energy to allow electrons and holes to cross the p-n junction such that a resulting recombination of electrons and holes cause emission of radiation.
• Advantages of LEDs over other excitation energy sources include small size, low power consumption, long lifetimes and low amounts of thermal energy emitted. In addition, LEDs have small dimensions that allow miniaturization of devices.
• the common LED is a blue LED.
• each phosphor is capable of being excited by a common LED which emits radiation at a wavelength from about 450 nm to about 480 nm. It has been found that color rendering can decrease at excitation energies below 450 nm whereas absorption by the phosphors decreases at excitation energies greater than 480 nm.
• An example of a blue LED that emits radiation in the above-mentioned energy ranges is a (In,Ga)N diode.
• a blue light source can provide inherent advantages over UN excitation sources in that power efficiency is increased for red and green phosphors excited by blue light.
• the present phosphor materials generally require lesser Stokes shifts than phosphors of the previous devices.
• certain tri-color prior art fluorescent lamps incorporate mercury plasmas which provide a UV emission centered at approximately 4.9 eV. This UV light excites blue, red and green phosphors such that resulting emission spectra show maximum intensities at energies of approximately 2.8 eV (unabsorbed light), 2.3 eV (green) and 2.0 eV (red) respectively.
• Significant Stokes shifts are obviously involved in this situation. Power efficiency, however, is limited by quantum deficit, which is the difference of the quantum energies of exciting and emitted quanta.
• Phosphors comprise host materials and dopant ions.
• the host material has an inorganic, ionic lattice structure (a "host lattice") in which the dopant ion replaces a lattice ion.
• the dopant is capable of emitting light upon absorbing excitation radiation. Ideal dopants strongly absorb excitation radiation and efficiently convert this energy into emitted radiation.
• the dopant is a rare earth ion. Rare earth ions absorb and emit radiation via 4f-4f transitions, i.e. electronic transitions involving f- orbital energy levels.
• the emissions of certain dopants can be shifted in energy depending on the host lattice in which the dopant ion resides.
• this aspect of the invention lies, in part, in the discovery that certain rare earth dopants efficiently convert blue light to visible light when incorporated into an appropriate host material.
• the first and second phosphors comprise a host sulfide material, i.e. a lattice which includes sulfide ions.
• Preferred host sulfide materials include CaS, SrS and a thiogallates such as SrGa 2 S 4 .
• Another advantageous feature of the present invention is to provide a phosphor mixture excitable by one common blue energy source of a relatively narrow linewidth, to emit light at two different energy ranges (e.g. red and green).
• Strategies to provide appropriate phosphors are disclosed here.
• the dopant is the same in the first and second phosphor.
• the red and green emissions of the two phosphors can be tuned by selecting an appropriate host material.
• the green phosphor is SrGa 2 S 4 :Eu.
• the red phosphor is selected from the group consisting of SrS:Eu and CaS:Eu.
• FIG. 1 is an overlay of emission spectra from two different phosphors having the same dopant capable of being excited by one common (In,Ga)N LED at 460 nm.
• the phosphors are provided as a mixture in an encapsulant.
• the spectra have been normalized to an intensity of 1.
• Spectrum 2 corresponds to an emission of the blue LED with a maximum intensity at ⁇ 460 nm
• spectrum 4 corresponds to an emission from a green phosphor material
• spectrum 6 corresponds to an emission from a red phosphor material
• the first and second phosphors can have different dopants.
• the same host material can be used, or the first and second phosphors can have different host materials.
• One of ordinary skill in the art can screen potential phosphor candidates by selecting phosphors that can be excited by radiation between about 450 nm and about 480, and observing whether they emit red or green light.
• the amount of dopant present in the host lattice is from about 0.1 mol% to about 8 mol%.
• Preferred amounts of dopant may depend on the type of host lattice.
• a dopant concentration in SrGa 2 S 4 is preferably from about 2 mol% to about 4 mol%, whereas a dopant concentration in SrS is preferably from about 0.3 mol% to about 0.8 mol%.
• the present invention also relates to another tri-color system, in which a first phosphor is excited by an LED source, and the emission of the first phosphor is capable of exciting a second phosphor.
• another aspect of the present invention provides a mixture of a first phosphor and a second phosphor, each phosphor comprising a host material and a rare earth dopant.
• the first phosphor is capable of being excited by a light emitting diode and the second phosphor is capable of being excited by an emission of the first phosphor.
• the LED is a blue LED.
• the first phosphor can be a green phosphor with an emission capable of exciting a red phosphor (second phosphor). This aspect allows the use of only one LED source in the event that only one phosphor is capable of being excited by the LED.
• Another aspect of the present invention provides a device comprising a phosphor mixture, as described previously, and a light emitting diode.
• the LED emits a local light pattern, the pattern defining either a volume or an area of light.
• a composition comprising a mixture of a first phosphor and a second phosphor is positioned in the light pattern.
• Each phosphor comprises a host sulfide material and a rare earth dopant, having compositions and concentrations as described previously. This arrangement allows light emitted from the LED to: (1) be absorbed by the composition; and (2) mix effectively with light emitted from the phosphor mixture such that good homogeneity of color rendering is achieved. This arrangement eliminates unwanted "demixing" of the various light sources.
• the device is a lamp.
• the lamp emits white light.
• the first phosphor is a green phosphor and the second phosphor is a red phosphor, where the white color is achieved by effectively mixing the green and red light with unabsorbed blue light provided by the LED.
• the lamp containing the phosphor mixture comprises a 5 mm LED lamp design of Hewlett-Packard.
• the white light lamp of the present invention is particularly advantageous in that the color rendering properties are far superior than those of any previous white lamps.
• the lamp is capable of emitting radiation having a color rendering index, Ra of at least about 60 at a color temperature from about 2700 K to about 8000 K, preferably an Ra of at least about 70, more preferably an Ra of at least about 80 and even more preferably an Ra of at least about 90.
• the lamp generates a CRI, Ra of greater than 70 for CCT values of less than 6000 K.
• FIG. 2 shows a simulation of emission spectra of a tri-color lamp comprising a mixture of SrGa 2 S 4 :Eu and SrS:Eu phosphors excited by a blue (In,Ga)N LED at 460 nm. Emission intensity or radiance is indicated in the ordinate axis.
• This system exhibits superior color rendering properties over a wide range of color temperatures.
• Spectrum 10 (3000 K), spectrum 12 (3800 K) and spectrum 14 (4400 K) each correspond to an Ra of 94 whereas spectrum 16 (4900 K) corresponds to an Ra of 92.
• Ra values of greater than 90 for white LEDs have not been previously observed. It is a feature of the present invention to mix respective amounts of the phosphors and to illuminate these phosphors with a blue LED to closely match these desired simulated spectra.
• the device can be designed to have desired characteristics depending on a particular application. For example, certain devices may be required to generate light of high intensity and only adequate color rendering is needed, whereas other applications may require high color rendering properties, at the expense of efficiency. Alternatively, color rendering can be sacrificed for higher efficiency. For example, a 50% increase in efficiency can be achieved by decreasing Ra down to about 60.
• Such properties can be varied by changing relative power fractions of each light source.
• a "power fraction" is the fraction of light from each source that provides the final light color. Power fractions can be varied by, for example, changing a relative amount of phosphor material present in the device, varying dopant concentration or changing the host lattice or dopant.
• the phosphor mixture can comprise more than two phosphors, so long as optimal color rendering properties are achieved.
• the device further comprises a polymer for encapsulating the phosphor composition.
• the phosphor mixture should exhibit high stability properties in the encapsulant.
• the polymer is optically clear to prevent significant light scattering.
• the polymer is selected from the group consisting of epoxy and silicone.
• Encapsulation can be performed by adding the phosphor mixture to a liquid that is a polymer precursor.
• the phosphor mixture can be a powder. Introducing phosphor particles into a polymer precursor liquid results in formation of a slurry (i.e. a suspension of particles). Upon polymerization, the phosphor mixture is fixed rigidly in place by the encapsulation.
• both the composition and the LED are encapsulated in the polymer.
• grain sizes are less than about 15 ⁇ m, and more preferably, less than about 12 ⁇ m, to avoid clogging of devices which dispose the phosphors.
• the grain size of each phosphor type varies.
• the grain size of SrGa 2 S 4 :Eu is less than about 10 ⁇ m and the grain size of SrS:Eu is less than about 12 ⁇ m.
• Other devices, however, can be prepared with larger grain sizes.
• the LED and composition are positioned within a reflector cup.
• a reflector cup can be any depression or recess prepared from a reflecting material. By positioning the LED and phosphor particles in a reflector cup, unabsorbed unmixed LED-emitted light can be reflected either back to the phosphor particles to eventually be absorbed, or mixed with light emitted from the phosphors.
• FIG. 3 shows a schematic of the device of the present invention.
• Lamp 20 comprises LED 22.
• LED 22 is positioned in a reflector cup 28.
• LED 22 emits light in a pattern indicated by lines 26.
• a phosphor mixture 24 is positioned in the pattern 26. It can be seen that some unabsorbed light emitted by LED 22 can reflect from walls of reflector cup 28 and back to phosphor mixture 24.
• reflector cup 28 can modify light pattern 26 if light is reflected into a space not previously covered by the initial light pattern (e.g. in the case of a parabolic reflector). It is understood that one of ordinary skill in the art can provide reflector cup 28 in any shape that optimizes reflection of light back to mixture 24, or optimizes positioning of LED 22 to provide a light pattern for efficient conversion.
• the walls of reflector cup 28 can be parabolic.
• Green LEDs have been developed only recently. Current green LEDs, however, are notoriously more inefficient than blue LEDs. In addition, emitted radiation from green LEDs exhibits wavelength shifts with an increase in temperature, which is an undesired characteristic.
• this aspect of the present invention provides a device comprising a green phosphor and a blue light emitting diode, for providing an excitation radiation to the phosphor.
• the blue light can be converted to green light via the green phosphor.
• This device is comparable to a green LED yet eliminates the disadvantages of green LEDs, such as providing comparable efficiencies to blue LEDs and minimizing radiation energy shifts with increasing temperature.
• the green phosphor is SrGa 2 S 4 :Eu. High luminous equivalents values of ⁇ 575 lm/W can be achieved with this phosphor at a maximum wavelength of about 535 nm, which is far superior to any other green LED or alternative. High absorption of excitation radiation is preferred to eliminate a significant amount of blue LED radiation which may spoil efficiency and/or color saturation.
• Example 1 Preparation of SrGa7S :Eu and SrS:Eu Phosphor Mixture SrGa 2 S 4 :Eu was produced by the method of P. Benalloul, et al., J. Alloys Compounds 227 (1998), 709, and references cited therein.
• the powders of the two phosphors are stirred in weighted amounts, which correspond to the desired power fractions of the three colors, into a liquid polymer precursor.
• a preferred polymer precursor is a standard precursor for 5 mm LED lamps, 'Hysol ST'.
• Example 2 Adjusting power fractions This example illustrates a method for adjusting power fractions at desired correlated different color temperatures, and these power fractions are listed in Table 1.
• a first approximation is made about respective power fractions of each color to obtain a desired spectrum that will result in optimal CCT/ CRI values. This is achieved typically by performing a best estimate of the respective weights of the two phosphors.
• the mixture is then prepared and the mixture is illuminated with the LED. In this example, the wavelength of radiation is 460 nm. A trial spectrum is then obtained.
• the first trial spectrum does not achieve the CCT/CRI values of the desired spectrum, small amounts of the appropriate phosphors can be added and a new trial spectrum can be obtained. This step is repeated until the trial spectrum closely matches the desired spectrum.
• Table 1 is generated by adding spectra of the three components: the LED, SrGa 2 S 4 :Eu, and SrS:Eu, with respective coefficients which correspond tot he power fractions.
• a composite spectrum is then obtained.
• the composite spectrum is evaluated using CIE recommended software (e.g. CIE 13.3-1995) for calculating CCT and CRI values.
• CIE recommended software e.g. CIE 13.3-1995
• CIE 13.3-1995 CIE 13.3-1995
• Table 1 shows example power fractions for the phosphor mixture of Example 1.
• the luminous equivalent of the resulting emitted light is about 310 ( ⁇ 4) lm/W.
• Example 3 5 mm LED LAMP An example of a lamp of the present invention is described here.
• An Hysol ST slurry comprising a phosphor mixture of 7.6 wt% of SrGa 2 S 4 :Eu and 10.4 wt% SrS:Eu was positioned in a reflector cup in a 5 mm lamp design of Hewlett-Packard.
• the average particle size of SrGa 2 S 4 :Eu was about 9 ⁇ m and the average particle size of SrS:Eu was about 11.5 ⁇ m.

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